CN101733141B - Catalytic cracking catalyst and preparation method thereof - Google Patents
Catalytic cracking catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN101733141B CN101733141B CN2008102269233A CN200810226923A CN101733141B CN 101733141 B CN101733141 B CN 101733141B CN 2008102269233 A CN2008102269233 A CN 2008102269233A CN 200810226923 A CN200810226923 A CN 200810226923A CN 101733141 B CN101733141 B CN 101733141B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- weight
- ludox
- acid
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to a catalytic cracking catalyst and a preparation method thereof. The preparation method of the catalyst comprises the following steps of: leading soluble glass and acid to contact to prepare alkaline silicasol with the PH value of 10-11.5 and the SiO2 content of 3-20wt%, mixing the alkaline silicasol and active components, pulping and drying. The pore volume of the cracking catalyst prepared by the preparation method of the catalyst in the invention is higher. The catalyst of the invention has higher capability of heavy oil cracking for catalyzing and cracking the heavy oil.
Description
Technical field
The present invention relates to a kind of hydrocarbon oil catalytic cracking Catalysts and its preparation method.
Background technology
In recent years, catalytically cracked material is heaviness, poor qualityization day by day, and this causes the coking yield of catalytic cracking higher, yield of light oil is on the low side, needs the Cracking catalyst of the low coking yield of high yield of light oil for this reason.Generally speaking, with respect to aluminium-based catalyst, the Silicon-rich Cracking catalyst has coke selectivity preferably.Preparation Silicon-rich Cracking catalyst is used silica sol binder always at present.
U.S. Pat P3867308 discloses by sodium metasilicate and inorganic acid reaction and has prepared acidic silicasol; And then be the method for adhesive preparation catalytic cracking catalyst with the Ludox, but prepared catalyst buildup density is big, is unfavorable for fluidisation; And pore volume is little, is unfavorable for the catalytic cracking of residual oil.
Disclose the method for preparing modified silicasol with aluminum sulfate solution among the U.S. Pat P3957689, the pH value of the mixed solution reduction sodium silicate solution through adding sulfuric acid and aluminum sulfate has improved the stability of Ludox.But prepared catalyst exists bulk density big equally, the problem that pore volume is little.
The Ludox that U.S. Pat P3972835 discloses dilution obtains low sodium Ludox through storng-acid cation exchange resin, and recycle silicon colloidal sol prepares the method for catalyst.But the preparation of low sodium Ludox need be through ion-exchange, and the preparation process is complicated, and cost is higher.
U.S. Pat P5961817 and USP6022471 disclose the method that Ludox that the Ludox that obtained by ion-exchange and acidization obtain prepares catalyst; To process slurries by Ludox and clay, the molecular sieve of ion-exchange preparation earlier in this method; Mix with the acidic silicasol that is prepared by sodium metasilicate, sulfuric acid, aluminum sulfate then, preparation technology is complicated.
CN1552801A discloses a kind of catalytic cracking catalyst that contains silica sol binder and preparation method thereof, the compound binding agent matrix that it adopts silica sol binder matrix or Ludox to combine with part peptization boehmite.
CN1749364A discloses a kind of Cracking catalyst of using silicon bonding; The method that this catalyst adopts colloidal sol and gel phase to combine; Before shaping of catalyst, keep slurries to be in dissolved colloidal state, generate the microspheroidal gel through control spray-drying exhaust temperature, the reaming of wearing out again processing obtains.
More than in the siliceous matrix cracking method for preparing catalyst, use acidic silicasol, prepared catalyst buildup density is big, pore volume is little.And the acidic silicasol complicated process of preparation need be regulated pH value in the preparation process repeatedly, and acid consumption is big; This Ludox stable poor, comparatively responsive to temperature, when temperature is higher than 30 ℃; The stability of Ludox descends greatly; Mix back gelling easily with matrix such as molecular sieve, boehmites, influence is produced, and the structure of the sour environment of acidic silicasol meeting saboteur sieve.
Summary of the invention
The technical problem that the present invention will solve is to the existing low deficiency of silica-based Cracking catalyst pore volume with the acidic silicasol adhesive preparation, and a kind of new Silicon-rich Cracking catalyst and preparation method thereof is provided.
The present invention provides a kind of preparation method of Cracking catalyst, may further comprise the steps:
(1) inorganic acid is mixed with water glass solution obtain Ludox, it is 10～11.5 that the consumption of acid and waterglass makes the pH value of the Ludox that obtains, SiO in the Ludox
2Content be 3～20 weight %;
(2) Ludox with step (1) mixes with molecular sieve, making beating;
(3) with the slurry dried of step (2), reclaim catalyst.
The present invention also provides a kind of Cracking catalyst, it is characterized in that, the method preparation that said catalyst is provided by the invention described above.
The present invention is 10～11.5 through the pH value of control waterglass and acid reaction; Obtained a kind of alkaline silica sol; It is stable that this alkaline silica sol can keep in wider temperature range, and with after other component is mixed, still can keep stable; Do not pay particular attention to and frequent pH value of regulating slurries; PH value requirement to other component is not the slurries stability height that so strict, prepared slurries stability is mixed with by acidic silicasol and matrix, active component, is not easy gelling more.Compare with the preparation acidic silicasol, the preparation technology of Ludox of the present invention is simple, can practice thrift the consumption of acid, and prepares Ludox with lower-cost waterglass and inorganic acid reaction, thereby can reduce cost, and reduces the pollution to environment.Method for preparing catalyst of the present invention is simple, does not need the particular processing process after the moulding.Compare with the catalyst that with the acidic silicasol is adhesive preparation, the catalyst of the inventive method preparation contains more middle macropore, has bigger pore volume and lower bulk density, helps the macromolecular cracking reaction of heavy oil.Prepared catalyst heavy oil cracking ability is strong, and coke selectivity is good, and gasoline selective is good.In catalyst preparation process, introduce aluminium oxide, can improve the cracking activity of matrix.
The present invention prepares the catalyst method can directly utilize the NaY molecular sieve, needn't worry the slurries saboteur sieve of low pH value, and can not influence the sodium ion exchange in the molecular sieve.
The specific embodiment
In the method for preparing catalyst provided by the invention; In the step (1) water glass solution is obtained Ludox with sour the contact; To make the pH value of resulting Ludox be 10～11.5 to the consumption of water glass solution and acid, and the pH value of preferred Ludox is 10.2～11.3, more preferably 10.8～11.2.Cross when low when the concentration of silica in the prepared Ludox, the adhesive property of Ludox can reduce, and in the Ludox during excessive concentration of silica, the bad stability of formed Ludox, and gelling easily, and adhesive property also can descend, therefore, preferred SiO
2Concentration be 5～20 weight %, 5～15 weight % more preferably.
In the method for preparing catalyst provided by the invention, SiO in the said waterglass
2Concentration be preferably 3～20 weight %, 5～20 weight % more preferably; The modulus of waterglass preferably is no more than 4.2, and more preferably the modulus of waterglass is 2.6～3.5.
In the method for preparing catalyst provided by the invention, used acid is selected from acid commonly used in the existing Ludox preparation in the step (1), is preferably in the inorganic acid one or more, for example one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid.The concentration of acid is 1～50 weight %, is preferably 5～30 weight %.
Among the preparation method provided by the invention, said waterglass contact with acid, the alkaline silica sol that obtains can be under higher temperature stable existence, in 0～60 ℃ temperature range, have stablely preferably, thereby said contact can at room temperature be carried out.Preferred water glass is 0～45 ℃ with the temperature that acid contacts the Ludox that obtains.
Among the preparation method provided by the invention, step contacts waterglass described in (1) with inorganic acid, can be intermittent mode, also can be continuation mode.When intermittent mode is produced, preferably acid is joined in the water glass solution.
In the method provided by the invention, the consumption of waterglass should make the content of silicon bonding in the prepared catalyst meet the demands in the step (1), is benchmark with the weight of prepared catalyst, with SiO
2The content of counting silicon bonding in the prepared catalyst is 5～90 weight %, is preferably 5～40 weight %, more preferably 10～30 weight %.
In the method for preparing catalyst provided by the invention, in the step (2) Ludox of molecular sieve with step (1) preparation mixed making beating then.Said mixing is preferably molecular sieve pulp is added in the Ludox.Said molecular sieve is the molecular sieve that is customarily used in Cracking catalyst, one or more of faujasite, zeolite and β zeolite for example with MFI structure, and described faujasite is X and y-type zeolite for example, and described zeolite with MFI structure is the ZSM-5 zeolite for example.Y-type zeolite one or more among NaY, HY, REY, REHY, USY, REUSY, DASY, the REDASY for example more preferably.In said REY, REHY, REUSY or the REDASY zeolite, with RE
2O
3The content of the rare earth oxide of meter is 0.5～20 weight %.Weight with catalyst is benchmark, and it is 10～95 weight % that the molecular sieve that step (2) is introduced makes the content of molecular sieve in the catalyst, is preferably 10～60 weight %, more preferably 20～40 weight %.
Among the preparation method provided by the invention; Also can comprise one or several before in step (3) and introduce the step of matrix; Said matrix is selected from for example one or more in clay, the inorganic oxide of Cracking catalyst matrix commonly used; Weight with catalyst is benchmark, and the amount that said matrix is introduced is no more than 80 weight %.Said matrix can be before Ludox generates, generate in or generate the back and introduce, preferred substrate and active component be introducing after Ludox generates.When matrix is introduced after Ludox generates, can matrix be mixed, pull an oar with Ludox earlier, mix with molecular sieve then; Perhaps matrix is mixed making beating then with molecular sieve, Ludox; Also can earlier molecular sieve be mixed with Ludox and introduce matrix then.When matrix when being multiple, can introduce simultaneously, also can gradation introduce; Can solid, the form of solution or slurries introduces matrix.Described clay is selected from kaolin, halloysite, imvite, diatomite, galapectite, saponite, rectorite, sepiolite, attapulgite, hydrotalcite and the bentonite one or more; Weight with catalyst is benchmark; Said introducing makes the content of catalyst medium clay soil be no more than 70 weight %; Be preferably 10～60 weight %, more preferably 20～50 weight %.Described inorganic oxide is aluminium oxide, silica (for example silica gel), titanium oxide, zirconia, magnesia for example, is preferably alumina host.Described introducing inorganic oxide can be introduced inorganic oxide or precursors of inorganic oxides; For example said alumina host; Can be in hydrated alumina, the hydrated alumina with structure of similar to thin diaspore, hydrated alumina, hydrated alumina, aluminium colloidal sol, gama-alumina, η-aluminium oxide, θ-aluminium oxide and the χ-aluminium oxide one or more, be preferably hydrated alumina with structure of similar to thin diaspore with bayerite structure with gibbsite structure with a diaspore structure.Introduce alumina host, can improve the heavy oil cracking ability of catalyst.Weight with catalyst is benchmark, and said introducing makes in the catalyst alumina host in aluminium oxide contain and is no more than 40 weight %, preferably is no more than 20 weight %, more preferably 5～15 weight %.Ludox of the present invention is with after matrix and active component are mixed, and pH value changes less, because the variation of pH value causes that the possibility of slurries gelling is little.
In the method for preparing catalyst provided by the invention, the described drying of step (3) is a drying means commonly used during Cracking catalyst is produced, spray-drying for example, and the present invention does not have specific (special) requirements.
Among the preparation method provided by the invention, washing described in the step (3) is existing method, for example can be through catalyst microballoon that spray-drying is obtained with deionized water or sulfate of ammoniac solution washing, to remove impurity such as sodium oxide molybdena wherein.Recovery described in the step (3) comprises the step with the catalyst filtration after the washing, drying.
Among the preparation method provided by the invention, also can comprise the step of ion-exchange.Said ion-exchange can contact with catalyst with earth solution and exchange, so that in catalyst, introduce rare earth.
The pore volume of catalyst provided by the invention is preferably 0.45～0.64, and heap is than being preferably: 0.50～0.58.Weight with catalyst is benchmark, and said catalyst contains the clay of molecular sieve, 0～70 weight % of 10～95 weight %, with SiO
2The meter 5～90 weight % silicon bonding and with Al
2O
3The alumina host of meter 0～40 weight %; Preferably contain the clay of molecular sieve, 10～70 weight % of 10～60 weight % in the said catalyst, with SiO
2Silicon bonding and the alumina host of 0～30 weight % of meter 5～40 weight % more preferably contain the clay of molecular sieve, 20～50 weight % of 20～40 weight %, with SiO
2The silicon bonding of meter 10～30 weight % and the alumina host of 5～20 weight %.
Catalyst of the present invention is suitable for especially RFCC of hydrocarbon oil catalytic cracking; Said heavy oil is decompressed wax oil, reduced crude, decompression residuum, vacuum gas oil (VGO) for example; AGO (atmospheric gas oil), straight run gas oil, propane is light/in heavy deasphalted oil and the coker gas oil one or more.
Embodiment 1
Under 34 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.5kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 10.2kg decationized Y sieve water, following in stirring then to wherein adding the sulfuric acid solution 1.14kg that concentration is 25 weight %, obtain SiO
2Concentration 8 weight %, the Ludox of pH value 10.81.This Ludox is placed and a little flocculation occurred in 24 hours, does not form gel.
In 3.8kg decationized Y sieve water, add 3.2kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %), making beating makes kaolin slurry.
In 2.5kg decationized Y sieve water, add 2.1kg USY molecular sieve (catalyst Shandong branch company produces, solid content 84.9%), making beating obtains molecular sieve pulp.
Above-mentioned Ludox, kaolin slurry, molecular sieve pulp are mixed, stir, obtain the pH value and be 10.78 dissolved colloidal state catalyst slurry, with this slurries spray-drying, obtain the micro-spherical catalyst particle then.
With sulphur aqueous ammonium and deionized water washing, oven dry obtains catalyst, is numbered A.Catalyst A consist of 45 weight % kaolin, 30 weight % molecular sieves, 25 weight %SiO
2Binding agent.
Comparative Examples 1
This Comparative Examples prepares catalyst with acidic silicasol.
Getting temperature is 18 ℃ of concentration, 25 weight % sulfuric acid solution 3.5kg, and (catalyst Shandong branch company produces, and contains SiO with the 7.2kg sodium silicate
2Concentration 20%, modulus 3.2) mixes with 7.3kg decationized Y sieve water and dilute, be cooled to 18 ℃, stir then in the above-mentioned sulfuric acid weak solution of the slow adding of the sodium silicate that will dilute down, obtain SiO
2Concentration 8 weight %, the pH value is 1.55 Ludox.
In 3.6kg decationized Y sieve water, add 3.0kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %), making beating obtains kaolin slurry.Kaolin slurry is mixed stirring with the Ludox slurries.
In 2.3kg decationized Y sieve water, add 2.0kg USY molecular sieve (catalyst Shandong branch company produces, and solid content 84.9% is with embodiment 1), homogenizer fully disperses, and using the watery hydrochloric acid adjust pH is 3.5.
Molecular sieve pulp is joined in above-mentioned Ludox-kaolin slurry, stir, obtain the pH value and be 2.90 dissolved colloidal state catalyst slurry; With this slurries spray-drying; Obtain the micro-spherical catalyst particle, then catalyst granules is washed oven dry with sulphur aqueous ammonium and deionized water; Obtain catalyst, be numbered B.Catalyst B consist of 45 weight % kaolin, 30 weight % molecular sieves, 25 weight %SiO
2Binding agent.
Table 1 is the pore volume that catalyst A and contrast medium B water droplet method record, intensity that the fluidisation abrasion method records (abrasion index) and heap ratio.
Table 1
| Example number | The catalyst numbering | Pore volume/mlg -1 | Heap ratio/gml -1 | Abrasion index %h -1 |
| Embodiment 1 | A | 0.47 | 0.56 | 2.0 |
| Comparative Examples 1 | B | 0.35 | 0.68 | 1.8 |
Data by table 1 can be found out, compare with the catalyst that with the acidic silicasol is adhesive preparation, are that the catalyst of adhesive preparation has bigger pore volume and moderate bulk density with the alkaline silica sol.
Embodiment 2
(catalyst Shandong branch company produces, and contains SiO with the 7.8kg sodium silicate under 38 ℃
2Concentration 15%, modulus 2.8) mix with 10.0kg decationized Y sieve water, under agitation to wherein adding 15 weight % sulfuric acid 1.71kg, obtain SiO then
2Concentration 6 weight %, the Ludox of pH value 10.3.
In 4.1kg decationized Y sieve water, add 4.2kg imvite (southization Red Hill bentonite Co., Ltd produces, and solid content is 78.6 weight %), making beating obtains montmorillonite slurry.
In 2.65kg decationized Y sieve water, add DASY molecular sieve 1.63kg (catalyst Shandong branch company produces, solid content 91.8%), making beating obtains molecular sieve pulp.
Above-mentioned Ludox, montmorillonite slurry, molecular sieve pulp are mixed, stir, obtain the pH value and be 10.2 dissolved colloidal state catalyst slurry; With this slurries spray-drying; Obtain the micro-spherical catalyst particle, then catalyst granules is washed oven dry with sulphur aqueous ammonium and deionized water; Obtain catalyst, be numbered C.
Catalyst C consists of 55 weight % imvites, 25 weight % molecular sieves, 20 weight %SiO
2Binding agent.
Embodiment 3
Under 26 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO with the 7.2kg sodium silicate
2Content 20 weight %, modulus 3.2) mix with 6.3kg decationized Y sieve water, following in stirring then to wherein adding the sulfuric acid solution 1.2kg that concentration is 20 weight %, obtain SiO
2Concentration 10 weight %, the Ludox of pH value 10.88.
In 3.6kg decationized Y sieve water, add 3.0kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %), making beating obtains kaolin slurry.
In 4.2kg decationized Y sieve water, add DASY molecular sieve 2.75kg (catalyst Shandong branch company produces, solid content 91.8%), homogenizer fully disperses, and obtains molecular sieve pulp.
Above-mentioned Ludox, kaolin slurry, molecular sieve pulp are mixed, stir adding boehmite 2.2kg (Shandong Aluminum Plant produces, solid content 33%) down; Making beating obtains the pH value and is 10.86 dissolved colloidal state catalyst slurry, with this slurries spray-drying; Obtain the micro-spherical catalyst particle, then catalyst granules is washed oven dry with sulphur aqueous ammonium and deionized water; Obtain catalyst, be numbered D.Catalyst D consists of 35 weight % kaolin, 35 weight % molecular sieves, 20 weight %SiO
2Binding agent, 10 weight % alumina hosts.
Embodiment 4
(catalyst Shandong branch company produces, SiO with the 6.5kg sodium silicate under the room temperature
2Concentration 28.8 weight %, modulus 3.0) mix with 8.1kg decationized Y sieve water, in stirring the salpeter solution 2.3kg that adds concentration 6 weight % down, obtain SiO then
2The Ludox of concentration 11 weight %, pH value 11.02.
In 1.1kg decationized Y sieve water, add 0.9kg kaolin (China Kaolin Co., Ltd produces, solid content 84 weight %), making beating makes kaolin slurry.
(catalyst Shandong branch company produces, solid content 93.2 weight %, RE in the molecular sieve in 3.8kg decationized Y sieve water, to add 0.9kg REY molecular sieve
2O
3Content 15 weight %) and 2.4kg DASY molecular sieve (catalyst Shandong branch company produce, molecular sieve content 91.8%), making beating obtains molecular sieve pulp.
Above-mentioned Ludox, kaolin slurry, molecular sieve pulp are mixed, stir, obtain the pH value and be 10.99 dissolved colloidal state catalyst slurry; With this slurries spray-drying; Obtain the micro-spherical catalyst particle, then with catalyst granules sulphur aqueous ammonium and deionized water washing, oven dry; Obtain catalyst, be numbered E.
Catalyst E consists of 13 weight % kaolin, 54 weight % molecular sieves, 33 weight %SiO
2Binding agent.
Embodiment 5
Under 15 ℃ the room temperature, (catalyst Shandong branch company of China Petrochemical Industry produces, SiO to get the 6.4kg sodium silicate
2Content 28.8 weight %, modulus 3.0) mix with 4.3kg decationized Y sieve water, in stirring the hydrochloric acid solution 1.6kg that adds concentration 10 weight % down, obtain SiO then
2Concentration 15 weight %, the Ludox of pH value 11.17.
Add 2.5kg halloysite (China Kaolin Co., Ltd produces, solid content 74.0 weight %) at above-mentioned Ludox, making beating makes kaolin slurry.
In 3.6kg decationized Y sieve water, add 3.1kg NaY molecular sieve (catalyst Shandong branch company produces, solid content 78.2%), making beating obtains molecular sieve pulp.
Above-mentioned Ludox, kaolin slurry, molecular sieve pulp are mixed, stir, obtain the pH value and be 11.12 dissolved colloidal state catalyst slurry, with this slurries spray-drying, obtain the micro-spherical catalyst particle then.
With sulphur aqueous ammonium and deionized water washing, oven dry obtains catalyst, is numbered F.Catalyst F consists of 30 weight % kaolin, 40 weight % molecular sieves, 30 weight %SiO
2Binding agent.
The pore volume that table 2 is catalyst C, D, E, F water droplet method records and the heap ratio of catalyst.
Table 2
| Example number | The catalyst numbering | Apparent bulk density/gml -1 | Weeper volume/mlg -1 |
| Embodiment 2 | C | 0.58 | 0.45 |
| Embodiment 3 | D | 0.50 | 0.64 |
| Embodiment 4 | E | 0.52 | 0.52 |
| Embodiment 5 | F | 0.54 | 0.49 |
Embodiment 6～10
Respectively to above-mentioned catalyst A, C, D, E, F at 800 ℃, burin-in process 8h under 100% water vapor conditions estimates on ACE (fixed fluidized bed) device then, employed feedstock oil is decompressed wax oil, character is seen table 3.The reaction condition and the result of catalyst see table 4.
Comparative Examples 2
Method according to embodiment 6～10 is estimated catalyst B, and appreciation condition and result see table 4.
Table 3
| Project | Data | Project | Data |
| Density (20 ℃)/gcm -3 | 0.9044 | Condensation point/℃ | 40 |
| Index of refraction (20 ℃) | 1.5217 | Aniline point/℃ | 95.8 |
| Viscosity (100 ℃)/mm 2·s -1 | 9.96 | Boiling range/℃ | |
| Carbon residue/% | 3 | Initial boiling point | 243 |
| Element composition/wt% | 5％ | 294 | |
| C | 85.98 | 10％ | 316 |
| H | 12.86 | 30％ | 395 |
| S | 0.55 | 50％ | 429 |
| N | 0.18 | 70％ | 473 |
Table 4
Data by table 4 can find out that catalyst provided by the invention has higher conversion ratio and stronger heavy oil cracking ability, has the gasoline yield height simultaneously, the characteristics that coke selectivity is good.Added 10% boehmite among the catalyst D, the matrix activity of catalyst is improved, and heavy oil cracking ability is enhanced.
Claims (12)
1. the preparation method of a catalytic cracking catalyst may further comprise the steps:
(1) inorganic acid is mixed with water glass solution obtain Ludox, it is 10～11.5 that the consumption of acid and waterglass makes the pH value of the Ludox that obtains, SiO in the Ludox
2Content be 3～20 weight %;
(2) Ludox with step (1) mixes with molecular sieve, making beating;
(3) with the slurry dried of step (2), catalyst is reclaimed in washing.
2. according to the described method of claim 1, it is characterized in that the pH value of described Ludox is 10.2～11.3.
3. according to claim 1 or 2 described methods, it is characterized in that SiO in the described Ludox
2Content be 5～15 weight %, the pH value of Ludox is 10.8～11.2.
4. according to the described method of claim 1, it is characterized in that the temperature of the Ludox that step (1) obtains is 0～60 ℃.
5. according to the described method of claim 1, it is characterized in that SiO in the said water glass solution of step (1)
2Content be 3～20 weight %, the modulus of waterglass is 2.6～3.5.
6. according to the described method of claim 1, it is characterized in that the described acid of step (1) is one or more in hydrochloric acid, sulfuric acid, nitric acid and the phosphoric acid.
7. according to claim 1 or 6 described methods, the concentration that it is characterized in that said acid is 1～50 weight %.
8. according to the described method of claim 1, it is characterized in that step (3) also comprises one or several and introduce the step of matrix that said matrix is one or more in clay, inorganic oxide and the precursors of inorganic oxides before.
9. according to the described method of claim 8; It is characterized in that said precursors of inorganic oxides is boehmite, have the hydrated alumina of a diaspore structure, have in the hydrated alumina of gibbsite structure, the hydrated alumina with bayerite structure and the aluminium colloidal sol one or more; Said inorganic oxide is one or more in aluminium oxide, silica, magnesia, titanium oxide and the zirconia.
10. a Cracking catalyst is characterized in that, said catalyst is by each method that is provided preparation of claim 1～9.
11., it is characterized in that according to the described catalyst of claim 10, be benchmark with the weight of catalyst, contain the clay of molecular sieve, 0～70 weight % of 10～95 weight % in the said catalyst, with SiO
2The meter 5～90 weight % silicon bonding and with Al
2O
3The alumina host of meter 0～40 weight %.
12. claim 10 or 11 application of said catalyst in RFCC.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102269233A CN101733141B (en) | 2008-11-20 | 2008-11-20 | Catalytic cracking catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008102269233A CN101733141B (en) | 2008-11-20 | 2008-11-20 | Catalytic cracking catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101733141A CN101733141A (en) | 2010-06-16 |
| CN101733141B true CN101733141B (en) | 2012-07-04 |
Family
ID=42457471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2008102269233A Active CN101733141B (en) | 2008-11-20 | 2008-11-20 | Catalytic cracking catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101733141B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105983431B (en) * | 2015-02-09 | 2018-10-16 | 中国石油天然气股份有限公司 | A kind of preparation method of silicon substrate catalytic cracking catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135756A (en) * | 1989-03-10 | 1992-08-04 | Thiele Kaolin Company | Process for improving the physical and catalytic properties of a fluid cracking catalyst |
| CN1749365A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | Cracking catalyst using silicon adhesive and its use |
| CN1749364A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its use |
-
2008
- 2008-11-20 CN CN2008102269233A patent/CN101733141B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5135756A (en) * | 1989-03-10 | 1992-08-04 | Thiele Kaolin Company | Process for improving the physical and catalytic properties of a fluid cracking catalyst |
| CN1749365A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | Cracking catalyst using silicon adhesive and its use |
| CN1749364A (en) * | 2004-09-15 | 2006-03-22 | 中国石油化工股份有限公司 | Hydrocarbon cracking catalyst and its use |
Non-Patent Citations (2)
| Title |
|---|
| JP特开平7-51574A 1995.02.28 |
| 刘娟娟等.硅溶胶技术的进展及在裂化反应中的应用研究.《甘肃科技》.2008,第24卷(第19期),第36页右栏最后1段至第37页左栏第1段,第38页右栏第3段及图3. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101733141A (en) | 2010-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100562360C (en) | Be used to produce the catalyst of light olefin | |
| CN105772074B (en) | A kind of preparation method of catalyst for heavy oil catalytic cracking | |
| CN101134906B (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| CN101134905A (en) | Method for improving solid content of catalytic cracking catalyst slurry | |
| US6613710B2 (en) | Process for preparation of bi-functional fluid catalytic cracking catalyst composition | |
| JP2017501871A (en) | FCC catalyst composition containing boron oxide and phosphorus | |
| AU2014239739A1 (en) | Method for manufacturing catalytic cracking catalyst for hydrocarbon oil | |
| JP7064484B2 (en) | The process of degluing alumina for a flow catalyst | |
| CN105728014B (en) | A kind of preparation method of catalytic cracking catalyst | |
| US8940156B2 (en) | Thermochemical structuring of matrix components for FCC catalysts | |
| CN102430422B (en) | Catalytic cracking catalyst for producing low-carbon olefin and application thereof | |
| CN1311907C (en) | Cracking catalyst for petroleum hydrocarbon, and preparation method | |
| CN101733141B (en) | Catalytic cracking catalyst and preparation method thereof | |
| CN105983431A (en) | Preparation method of silicon-based catalytic cracking catalyst | |
| CN101745415B (en) | Alkaline silica sol composition and application thereof in preparation of cracking catalyst | |
| CN101745416B (en) | Catalytic cracking catalyst and preparation method thereof | |
| JPH08173816A (en) | Catalyst composition for fluidized catalytic cracking of hydrocarbon and its production | |
| CN113797962B (en) | Catalytic cracking auxiliary agent and preparation method and application thereof | |
| CN100429293C (en) | Process for preparing catalytic cracking catalyst | |
| CN111822033B (en) | Hydrocarbon oil catalytic cracking catalyst rich in naphthenic cyclic hydrocarbon, and preparation method and application method thereof | |
| CN100377782C (en) | Hydrocarbon cracking catalyst and its use | |
| CN1312255C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves | |
| CN107866211B (en) | TiO 22Sol and catalytic cracking catalyst and process for producing the same | |
| CN1332765C (en) | Process for preparing cracking catalyst for hydrocarbons containing molecular sieves | |
| CN101624536B (en) | Method for preparing catalytic cracking catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |